Faradaic double layer depolarization in electrokinetics: Onsager relations and substrate limitations

Leeuwen, Herman P. van; Duval, Jérôme F. L.

doi:10.1016/j.jcis.2007.02.014

Cited by 12 publications

(6 citation statements)

References 28 publications

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“…Also, their system ceases to be strictly linear for non-Newtonian fluids, as coefficient χ 11 will contain a pressure dependence. van Leeuwen and Duval [27] describe effects of a conductive substrate, where faradaic reactions are permitted, on the form of Onsager relations.…”

Section: Q/a I/amentioning

confidence: 99%

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Force and flux relations for flows of ionic solutions between parallel plates with porous and charged layers

Barbati

Kirby

2013

Phys. Rev. E

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We derive coefficients of the electrokinetic coupling matrix (χ(11), χ(12), and χ(21)) for the flow of an ionic solution through a parallel-plate geometry having porous and charged layers grafted onto a solid surface with a known potential and demonstrate Onsager reciprocity for the cross terms (i.e., χ(12)=χ(21)). Our results enable the prediction of system outputs in the solid-porous-fluid system from parameters that are either known or may be measured and inferred. These electrokinetic coupling coefficients are in terms of the potential, ϕ, and fixed charge, ρ(f), only, removing dependence on field gradients and fluid velocity. Additionally, we present simplified expressions of these coupling coefficients in limiting regions of the parameter space. Away from these limits, we present numerical results demonstrating the facility of our functional form for facile numerical approximation and report the utility and accuracy of our analytical approximations.

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Section: Q/a I/amentioning

confidence: 99%

“…The solution is most easily obtained by solving directly for the field u (e) from the Stokes equations with zero pressure forcing, a no-slip boundary, and symmetrical velocity profiles about the centerline (27) or…”

Section: Coupling Terms For Systems With Rigid Interfacesmentioning

confidence: 99%

Force and flux relations for flows of ionic solutions between parallel plates with porous and charged layers

Barbati

Kirby

2013

Phys. Rev. E

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“…These experimental and theoretical studies confirm the sensitivity of the ionic-current rectification to the surface charge distribution, especially near the tip. The ionic-current rectification phenomenon is actually one of the interfacial electrokinetic phenomena in nature, and many informative and interesting works on electrokinetics exist [26,32,[39][40][41][42][43][44][45][46][47].…”

Section: Introductionmentioning

confidence: 99%

Effect of linear surface-charge non-uniformities on the electrokinetic ionic-current rectification in conical nanopores

Qian

Joo

et al. 2009

Journal of Colloid and Interface Science

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“…It should also be added that depolarisation can be realized not only by electron transfer reactions (for metals), but also by ion transfer processes (in hydrogels and, more generally, soft surface layers [7][8][9][10][11]43]). The underlying Onsager relationships are laid out in [44] and highlight the common basis for suppression of streaming potential either by ionic or electronic conduction processes. Reference [44] further discusses possible limitations of double layer polarisation by faradaic processes due to the finite electronic conductivity operational in the bulk substrate, a matter that may be of particular importance in electrokinetics of some semi-conducting materials.…”

Section: Faradaic Double Layer Depolarisation In Electrokinetics: Onsmentioning

confidence: 99%

Coupling between electrokinetics and electrode kinetics by bipolar faradaic depolarisation processes in microfluidic channels

Duval

Leeuwen

2020

Advances in Colloid and Interface Science

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This article is concerned with the nature and impact of bipolar faradaic electron transfer processes in the context of measuring electrokinetic parameters at the interface between an electronically conductive substrate such as a solid metal layer, and a liquid medium. More specifically, it analyses the steady state electric current through the electrodic substrate layer in terms of its short-circuiting effect on the system's electrokinetic quantities, such as the streaming potential. Ample attention is paid to the electrodic behaviour of the chosen metal and its electron transfer characteristics with respect to redox functions in the medium. The electrochemical reversibility of redox couple species is expressed in terms of their oxidation and reduction rate constants as compared to their diffusive transport rates under lateral flow conditions. High values for rate constants lead to high reversibilities and large bipolar leaking currents through the metal substrate. In turn, high electron transfer rate constants generate large reductions in measured values for electrokinetic quantities such as streaming potentials that become a non-linear function of the pressure gradient applied through the fluidic chamber. The present article presents an overview of theoretical and experimental approaches of this intricate coupling between bipolar electrode kinetics and electrokinetics and the impact from Hans Lyklema's contributions. It highlights not only the implications of bipolar faradaic depolarisation processes in electrokinetics but also the importance of bipolar electrochemistry principles in various electroanalytical applications reported for e.g. the control of microfluidic flows, for surfaces functionalisation, particles manipulation or for the wireless detection of electroactive analytes.

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Faradaic double layer depolarization in electrokinetics: Onsager relations and substrate limitations

Cited by 12 publications

References 28 publications

Force and flux relations for flows of ionic solutions between parallel plates with porous and charged layers

Force and flux relations for flows of ionic solutions between parallel plates with porous and charged layers

Effect of linear surface-charge non-uniformities on the electrokinetic ionic-current rectification in conical nanopores

Coupling between electrokinetics and electrode kinetics by bipolar faradaic depolarisation processes in microfluidic channels

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